Palladium compositions suitable as oxidation catalysts

ABSTRACT

HOMOGENEOUS AND HETEROGENEOUS CATALYSTS SYSTEMS CONTAINING CERTAIN PALLADIUM (II) SALTS AND COPPER (II) SALTS HAVE BEEN DEVELOPED. A SPECIFIED BALANCE OF A COPPER (II) HALIDE AND OF A NON-HALIDE COPPER (II) SALT IS MAINTAINED.   THE CATALYSTS ARE EFFECTIVE FOR OXIDIZING CO TO CO2 AND SO2 AND SO3.

Feb. 5, 1974 w, LLOYD E-rAL 3,790,662

PALLADIUM COMPOSITIONS SUITABLE AS OXIDATION CATALYST Filed Feb. 7, 1972 Effect of Copper(li) Chloride Copper(ll) Nitrate Rofio Upon Efficiency of Cofolysf Solutions- Percent Copper (I l) Nitro're of Total Copper Solis 0.004 M Pd 01 0 O O O O @26 S 2 @265 5560 6 5 6260 86 80 I00 Percent Copper (I I) Chloride of Total Copper Solis (Tofol Copper Solt Concentration LOO Moles per Lifer) United States Patent Office 3,790,662 Patented Feb. 5, 1974 US. Cl. 423-437 15 Claims ABSTRACT OF THE DISCLOSURE Homogeneous and heterogeneous catalysts systems containing certain palladium (II) salts and copper (II) salts have been developed. A specified balance of a copper (II) halide and of a non-halide copper (II) salt is maintained. The catalysts are effective for oxidizing CO to CO and S02 and S03. I

FIELD OF INVENTION This invention has to do with compositions containing a palladium (II) salt, a copper (II) halide and a non-halide copper (II) salt. The compositions are effective oxidation catalysts, particularly for the oxidation of CO to CO and 50;, to S BACKGROUND OF INVENTION In recent years, considerable attention has been given to methods for removing CO and SO fr m our environment. CO is a pollutant, particularly as an exhaust product from motor vehicles. Nationally the transportation industry is responsible for 42% of the total air contaminants emitted to the atmosphere; and carbon monoxide, a colorless, odorless and lethal gas, being one of the major components of automobile exhausts 'is the largest single air pollutant. Of the 90.5 million tons of carbon monoxide emitted in 1968 to the atmosphere, 63.8 million tons or. 71% came from transportation activities. S0 is also a pollutant, but generally as a product from the burning of relatively high sulfur heating oils and coals.

The oxides of sulfur on a national basis in 1968 accounted for an estimated 33 million tons, or 15-16% of the total emitted air contamination. Of this, fuel combustion by stationary sources accounted for 24.4 million tons or 74% of the total oxides of sulfur. The most important air pollutants among the oxides of sulfur are sulfur dioxide, S0 and sulfur trioxide, S0 The estimate ratio of S0 to S0 in the atmosphere of Chicago is 100:1. The conversion of S0 to S0 in air is very slow. The major source of S0 is from the combustion of sulfur-containing fuels.

Many catalysts and combinations of catalysts have been proposed to convert CO to CO and/or S0 to 80;, or sulfuric acid. These have suifered from a variety of disadvantages, including high cost, high susceptibility to poisoning and short catalyst lifetimes, low conversion rates at low temperatures or at low flow rates or at low concentrations of the contaminant gas, high head loss, and undesirable side reaction products. For example, a copper chromite catalyst in the presence of water vapor converts nitrogen oxides to ammonia; an irQnoxide-iron sulfate catalyst emits hydrogen sulfideyuranium on alumina is not effective at low CO concentrations; manganese oxide is unsuited to high-temperature operation; hopcalite catalysts are'poisoned by water vapor.

Most of the known art of palladium-catalyzed oxidations is directed to the oxidation of olefins to carbonyl compounds, mainly acetaldehyde and ketones. This reaction, as well as the palladium (II) chloride oxidation of CO, was first reported by F. C. Phillips (Z. anorg. Chem, 6, 229 (1894).

Dragerwerk (German 713,791) shows the successful incorporation of palladium (II) chloride and copper (II) chloride to obtain the catalytic oxidation of CO using atmospheric oxygen as the ultimate oxidant. Thus Example 1 uses a dilute hydrochloric acid solution of PdCl and CuCl and, like Phillips, recommends elevated temperatures (80100 C.). Both Phillips and Dragerwerk worked with halide salts, and both found it desirable to operate at somewhat elevated temperatures in order to overcome the sluggishness of the reaction at ambient temperatures. This has also been observed in more recent studies by Markov (V. D. Markov and A. B. Fasman, Zh. Fiz. Khim., 40, 1564 (1966); V. D. Markov, V. A. Golodov, and A. B. Fasman, Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk, 1968, 36), who worked with excess chloride or bromide ions present and who found the reaction between Pd(II) and Co to be so slow as to be the rate-determining step of the overall reaction.

Lloyd (US. 3,410,807) has described the chemistry of homogeneous solutions of palladium (II) and copper (II) salts in alcoholic solvent-media. In substantially dry alco holic systems (less than 2% water), CO is reacted with the alcohol solvent-reactant to synthesize organic carbonate esters; similarly, SO is reacted to synthesize organic sulfate esters. For the purposes of air pollution control and abatement, these reaction systems would release exit gas streams saturated with the volatile alcoholic solventreactant, and would be unacceptable from both an economic and environmental standpoint, and in the case of OO oxidation would require side-stream removal of the carbonate ester formed in the reaction.

The first reported supported catalytic oxidation of CO with Pd(II) and Cu(II) appears in the Dragerwerk patent. More recent work with supported palladium catalysts makes use of zerovalent palladium metal and, typically, copper oxides upon alumina or silica support. It should be noted that, although some of this literature makes use of palladium (II) chloride and copper (II) chloride in catalyst preparation, it is usually explicitly evident and is always implicitly evident from a consideration of the thermal stabilities and properties of the inorganic compounds involved, that the actual catalyst involves palladium '(0) and a mixture of copper oxides and basic copper choride. For example, Keggi (French 1,539,443) treats an inert support with a solution containing palladium (II), copper (II), and aluminum (III) chlorides, dries the support, then calcines at 600 C. for two hours At this temperature, well above the decomposition temperature of palladium (II) chloride, PdCl is reduced to Pd(O'). This temperature is also well above the melting point of copper (II) chloride and the sublimation temperature of aluminum (III) chloride. Indeed, as Keggi reports, the total concentration of chloride remaining on and in the calcined catalyst is very low.

The present invention is directed to the provision of new and superior oxidation catalysts, which are particu- In accordance with the present invention, there are provided oxidation catalysts comprising aqueous homogeneous solutions containing specified proportions of a water-soluble palladium (II) salt, a copper (II) halide, a copper (II) salt of an oxyanion derived from a strong acid, and the balance substantially water. There are also provided heterogeneous oxidation catalysts comprising specified proportions of the water-soluble palladium (II) salt, the copper (II) halide and the other copper (II) salt, with or without an appropriate carrier. 7

There are also provided processes for oxidizing CO and S to CO and S0 respectively, by contacting a gaseous charge containing C0 and/ or 50;; with a catalyst of the character specified above.

Y SPECIFIC EMBODIMENTS OF THE INVENTION As indicated above, the compositions of this invention contain a water-soluble palladium (II) salt. Typical of such salts are the: chloride, bromide, nitrate, sulfate and Li PdCl Particularly preferred is palladium (II) chloride.

The concentration of the palladium (II). salt in the homogeneous solutions can range from at least about 0.00005 mole per liter to the solubility of the salt in water. Preferred concentrations range from about 0.001 to about 0.02M.

A mixture of copper (II) salts (b) and (c), is em- .ployed. One salt (b) is a halide, namely the chloride or bromide. The chloride is preferred. The other salt (c) is a nonhalide, and is a salt of an oxyanion derived from a strong acid. Typical of (c) are: nitrate, sulfate, alkylsulfonate (e.g. methanesulfonate), trifiuoromethanesulfonate), aryl sulfonate (e.g. p-toluenesulfonate, tetrafluoroborate, perchlorate, trifiuoroacetate, trichlo'roacetate and methanephosphonate.

The total concentration of the copper (II) salts (b) and (c) ranges from about 0.003 to about 3, and pref.- erably 0.1 to 2.0 moles per liter. Solutions with very low copper (II) concentrations, below 0.003 M, are limited in the rate at which reduced palladium (0) can be re' oxidized, and in unfavorable operating conditions may precipitate reduced palladium metal, removing it from the homogeneous system with consequent loss ofcatalytic activity. At copper (II) salt concentrations above about 3 moles per liter two disadvantageous factors emerge: increased solution viscosity which impairs the ease and efliciency of gas-liquid mixing, and the possi* bility of exceeding salt solubilities and precipitatingcatalyst or cocatalyst under actual operating conditions in which water evaporation may involve fluctuations in water content.

A critical relationship of the aqueous homogeneous catalysts is the balance of copper (II) halide (b) and the other copper (II) salt (c). It has been found'that superior results are realized by employingfrom about to about 80, and preferably -60, mole percent'of salt (b) of the total of (b) and (c), with (a) there mainder.

Stated in another manner, the approximate concentration relationships of the several components are as follows:'

The chloride ion concentration is 0.1-0.9, preferably 0.2-0.7, times the weight of copper (II); or, when brothe coiiversion of C0 is co, and so,

mide ion is present instead of chloride ion, the bromide ion concentration is 0.25-2, preferably 0.4-1.5, times the weight of copper (H) present.

As mentioned above, the palladium (II) salt can be in the form of Li PdCl Thus, LiCl in association with PdCl serves to facilitate dissolution of PdCl in water. In this regard, it has been found that when PdCl and LiCl are added to a solution containing copper (II) salts (b) and (c), the resulting solution is eflective as an oxidation catalyst; however, when the resulting solution is allowed to age at ambient temperature (2025 C.) for about three hours or more, it is substantially more effective as an'oxidation catalyst.

In addition to the palladium (II) salt (a) and the copper (II) salts ('b) and (c), the homogeneous solutions can also contain a compatible chloride or bromide salt to aid in the dissolvingof the palladium (II) salt. Chloride and bromide salts of Group IA and Group IIA metals, for example, have no adverse effect upon the catalytic activity of the solutions. The solutions can also contain any other dissolved salts which are compatible with the palladium (II) and copper (II) salts, that is, which do not form specific complexes or precipitates of copper (II) or palladium (II). It should be noted that when a salt such as lithium salt is included, the halide/ nonhalide ratio, (b)/(c), applies to the total anion concentrations.

The solutions are prepared by adding the salts (a), (b) and (c), with or without a chloride or bromide salt of a Group IA and/or Group IIA metal, to water in the concentrations specified above. Other than the aging effect already mentioned with respect to a solution containing LiCl, the particular order of addition of salts (a), (b) and (c) to water has no substantial influence upon the catalytic effectiveness of the resulting solution.

When the homogeneous catalysts are employed for the oxidation of CO to CO and S0 to S0 the temperature used can be from about 0 C. to about 100 C., and preferably at l015 C., at atmospheric pressure. Variation in pressure can range from subatmospheric (the limit being the vapor pressure exerted by the catalyst solution) through to superatmosphcric, with the preferred pressure being at or near atmospheric pressure.

Flow rates depend upon the geometry of the apparatus employed. Contact time will range from about 0.1 second to about 5 seqpnds, with a preferred range of 0.3-3

seconds. I

The CO partial pressure can be any fraction of the total gas pressure. CO removal at partial pressures as reactant gases are 0-0.5 atmosphere.

If there shouldbe less than a stoichiometric excess of oxygen in the feed gas (with respect to CO and/or S0 then the catalyst solution should be contacted periodically with an oxygen-containing gas, such as air, in

order to reoxidize copper (I) and retain catalyst activity.

This can be done by continuous recyclingor batch treatment.-

The heterogeneous catalysts of this invention comprise a-support material impregnated with specified amount of the palladium (II) salt (a) and of the copper (II) salts (b) and (c). Here again, the Water-soluble palladium (II) salts (a) and copper'(II) salts (b) and (c), above, are employedfll'ypical supports include alumina, silica, silicaalumina, zirconia, thoria, aluminum silicates, zeo- 1 lites, magnesia, silicon carbide, and the like. Such supports are well known in the art andare available commercially. Particularly useful are those supports which can be used at temperatures generally existing in vehicle exhaust sys terns and industrial stacks.

"The supported catalysts are prepared by contacting an aqueous homogeneous solution with a suitable support, and slurrying the solution with the support at C.- 300 C., preferably 60150 C., for -60 minutes. The support which has becomeimpregnated with the solution is separated from the remaining solution, as by suction filtration, and is dried. Drying can be accomplished with an aspirator air stream for several minutes, then by keeping the impregnated support under vacuum (e.g. 20 mm.) at 20-25 C. for 16 hours, followed by abount 24 hours at 20 mm. vacuum at 60 C. There is no need to calcine the catalyst.

' The resulting supported catalysts will contain: at least about 0.00001, preferably 0.0003 to 0.03, gram-moles of palladium (H) salt per kilogram of inert support, and the total copper (II) salts from about 0.001 to about 1.5, preferably 0.03-0.8, gram-moles per kg., with the same approximate ratio of (b)/ (c) as specified above.

The concentration relations can also be expressed as:

0.001-10, preferably 0.3-3, grams of palladium (II) per kilogram of inert support,

0.06-100, preferably 2-50, grams of copper (II) per kilogram of inert support,

- 80, preferably -60, mole percent of copper (II) salt (b) of the total copper (II) salts.

The chloride and bromide concentrations are the same as those given above for homogeneous catalysts.

Here also a salt of a Group IA or Group IIA metal which does not cause precipitation of a copper or palladium salt, can be employed.

The heterogeneous catalyts can be employed in oxidation reactions, and particularly for converting CO to CO and S0 to S0 at temperatures of the approximate range of from about 0 to about 300 C., and preferably from ambient temperature to about 150 C.

Total pressure can be atmospheric, suband superatmospheric, with those approximating atmospheric being preferred.

With regard to gas flow rates, a minimum of about 0.1 second contact time is employed. An upper limit is governed by considerations of practical economics (and upon how rich the gas stream is in oxidizable contaminant gases). Preferred contact times range from 0.3 to 3.0 seconds.

rate was 640i40 mL/min. and the mean gas-liquid contact. time (based upon solution and overhead foam volumes) was 1.9i0.l sec. Samples of exit gas were collected at 9.0 minutes and again at 10.0 minutes after the gas flow was started; these were analyzed by quantitative gas chromatography for carbon monoxide and for carbon dioxide. The results, expressed for various aqueous solutions as percent conversion of CO to CO are shown in Table I below and in the drawing.

The aqueous solutions were prepared by dissolving PdCl LiCl, CuCl; and Cu(NO in water at about 20-25 C.

TABLE I CuClz C11(N03)2 Percent Total percent percent conver- Cu salt, of total of total sion of M PC1012, M LiCl, M Cu salt Cu salt CO to C02 1.00 0010 0020 100 Nil 1 Nil 0010 0020 80 20 1 Nil 0010 0020 40 0. 4 0010 0020 40 00 4. 2 0010 0020 20 80 58 0010 0020 Nil 100 1 Nil 0.97 0040 0080 100 Nil 26 0040 0080 80 20 41 0040 0080 60 40 72 0040 0080 40 60 a 85 0040 0080 20 80 3 78 0040 0080 Nil 100 0. 8

1 No detectable 00;; threshold of detection is 0.2% conversion level.

2 A white precipitate of cuprous hydroxide was formed aiter 10 minutes operation.

8 A white precipitate of cuprous hydroxlde and a dark precipitate of Pd and/or PdO was formed after 10 minutes operation.

Example 2 The apparatus and procedure of Example 1 was employed. Gas flow rate was regulated at 630:10 ml. of CO per minute. All runs were conducted at 23 C. LiCl concentration in each run was approximately twice the concentration of the palladium or rhodium chloride concentration.

PdCl was compared with RhCl Various combinations of cupric salts were used. Comparison is also given of ferric salts and of organic redox compounds, in place of the cupric salts.

Results are provided in Table II.

TABLE II Gas-liquid Percent contact time conversiocn o Pd or Ph Cupric salts, etc. Min Sec. Co,

Nil 011012, 0.50 M; Cu(N03)i, 0.50 M 1 5 1 Nil PdClz, 005 M CllClg, 0.5 M; CuSO4, 0.50 M 1 6 31 PdCl .005 M. CuBri, 0.50 M; Cu(NO3)2, 0.5 M 1 9 32 B11013, .005 M CuClz, 0.50 M; Cl1(N0a)2, 0.50 M 1 3 1 Nil PdClz, .005 M FeOla, 0.50 M; Fe(N03)3. 0.50 M 2 5 :04 PdClz. .005 M p-Benzoquinone 2.0 M in 1,2-propanediol 0. 4 PC1011, .0025 M p-Benzoquinone 1.0 M in a 1:1 mixture (VOL/vol.) of ethanol 2 15 and 1,2-propnnediol. PC1012, .005 M CuCl 0.50 M; C11(NO3)2, 0.50 M [fresh mixed with Pd salt]- 1 3 17 PdClz, .005 M 011012, 0.50M; Cl1(NQ3)g, 0.50M [after three hours standing]- 1 3 82 1 No detectable 00:; threshold of detection is 20.2%.

With employment of the heterogeneous catalysts, it is recommended that molecular oxygen also be included in 0 the reaction system. In order to have catalyst life-times of practical duration, molecular oxygen is present in at least stoichiometric quantities in the gas stream being treated.

ILLUSTRATIVE EXAMPLES The homogeneous solutions and oxidation reactions therewith, are illustrated by the following examples.

Example 1 To a 500-m. gas-scrubbing bottle fitted with a standard coarse glass diffusing frit was added 100 ml. of an aqueous solution. A mixture of helium 98% and carbon monoxide 2.00% was then passed through the diffusing frit at atmospheric pressure and at 23 C. The gas flow Example 3 A series of runs was carried out in which 1.5 liters of an aqueous solution was mixed vigorously with sulfur and titrated with standard base to determine acid normality.

Under this regimen the dissolved S0 is very substantially removed, so that in the case of no oxidation (see Run #1), the acid concentration in the degassed solution is very low. To the extent that oxidation of S0 has occurred, however, sulfuric acid will have been formed,

and this acid cannot be removed from aqueous solutions by any degassing technique. The extent of formation of sulfuric acid, as measured by the development of permanent acidity, measuresthe extent of oxidation of sulfur dioxide.

Run #1.-This run was carried out with 1.5 liters of water. The water was completely saturated with sulfur dioxide Within 15 minutes. After degassing, titration of aliquots with a standard base showed the residual acidity (due to sulfurous acid) to be 0.015 N (10.001).

Run #2.'Ihis run was carried out as Run #1, except that the water was replaced with 1.5 liters of an aqueous solution containing 0.50 M cupric chloride and 0.50 M cupric sulfate. After treatment as in Run#l, the gross titratable acidity was found to be 2.006 N (L -0.006). After correcting for the effective acidity of the cupric salts, the net gain-inacidity upon 20' minutes contact with S was 0.39 N.

Run #3. This was carried out in the same manner as Runs #1 and #2, except that the 1.5 liters of aqueous solution contained 3.55 X 10* M palladous chloride, 0.50 M eupric chloride, and 0.50 M cupric sulfate. The gross titratable acidity was found to be 2.641 N ($0.013), which after correcting for the etfective acidity of the salts showed a net gain of 0.96 N. This amount of formed acid is approximately 2% fold greater than that in Run #2 and approximately sixty-fold greater than that in Run #1.

Example 4 A stream of helium containing 2x10 ppm. CO was passed through an aqueous solution containing 0.020 M "PdCl 1.00 M CuCl and 1.00 M Cu(N0 In each of three standard gas-washing bottles (250 ml. capacity, fitted with coarse fritted glass diffusers) was placed 150 m1. of catalyst solution, and the three bottles were connected in series downstream of a fiowmeter connected to a cylinder containing the helium-carbon monoxide mixture. The cylinder valve was set to permit a how of 235 ml./min. through the system. After 25 min. of operation at 22 C., a portion of untreated feed gas was then collected for comparison.

The gas samples were analyzed by gas chromotograph, with a standard thermal conductivity instrument (Aerograph Model 202-1C) fitted with a 6 ft. x A in. column of Porapak Q for carbon dioxide assay and a 6 ft. x' flt' column of molecular sieve A for carbon monoxide assay, both determinations run at a column temperature at 30 C. Assays were made in quadruplicate, with retention of the best three of each set of four determinations.

Data is given below in Table III, showing'that the CO content of the gas mixture is reduced from 2.0 to 0.06%,

at the same time that a major CO peak appears, as a result of passage through the catalyst system. Cross analysis of the untreated gas shows the presence of a small amount of CO about 0.05%, as an initial impurity.

This study, with an effective gas-liquid contact time of about 1.5 sec., shows that a gas stream containing 2 x p.p.m. carbon monoxide can be treated to'eifect conversion of 97% of the CO to CO 7 (average 2.00%).

Norm-SD of analysis: overall=|=0.021% as CO (8 DE); low range i0.010% as CO (4 DF).

Heterogeneous catalysts and oxidation reactions therewith, are illustrated by the following examples.

Example 5 Four solid catalyst systems were prepared by contacting portions of an aqueous catalyst solution with each of the following: (a) Molecular Sieve 5A, a crystalline aluminosilicate marketed by Union Carbide; (b) silica gel; (0) activated alumina, and (d) activated charcoal Norit A" marketed by Matheson Coleman & Bell. The catalyst solution comprised: PdC1 0.01 M; LiCl, 0.02 M; CuCl 0.788 M; Cu(NO 0.98 M, and the balance water.

To SO-ml. portions of the above catalyst preparation solution were added 10.0-g. portions of each of several solid catalyst supports, described in Table IV below. The mixtures were slurried for 15 minutes at room temperature, then the solids were collected by suction filtration and dried for five minutes by an aspirator air stream. Then, the resulting moist cakes were broken up and the solids dried overnight at 20 mm. pressure. The solids were then further dried at 60 C. and 20 mm. pressure for an additional 24 hours. Each supported catalyst powder was then weighed to determine the amount of catalyst picked up, then packed into a copper column 36 inches long and 0.190 inch internal diameter, closed with loose glasswool plugs to prevent catalyst loss.

The pickup of weight for each of four catalyst supports, and the indicated concentrations of components per kilo: gram of catalyst support, is:

Wt. gain after Calculated concentrations, drying, gram-moles/kg. support per 10 g. oi Support support PdClz CllClz Cu(No LiGl Alumina 1. 0 0034 270 335 0068 Norit A- l. 0 0034 270 335 .0068 Molecular sieve. 2. 8 0096 755 93S 0190 Silica 2. 8 0096 755 938 0190 through a standard 500 oil. gas sparger containing 150 ml. of water, thus humidifying the gas mixture. The gas mixture was then passed through a section of copper tubing (36 inches by 0.250 inch outside diameter, 0.190 inch inside diameter, and with approximately 24 inches of the length packed with the solid catalyst-and-support combination being tested), and then to an exit vent from which samples were periodically withdrawn. For a control run with no supported catalyst, the exit sample was withdrawn immediately downstream of the humidifying gas sp-arger. Crude flow controls of the air and the helium-CO streams were accomplished by floating ball flowrneters; however, the actual amount of air in the gas mixture was determined more accurately in the course of gas chromatographic analysis of the exit gas samples. Y

Gas chromatographic analysis was obtained on samples collected in standard ml. gas collection flasks which were evacuated immediately prior to sampling. Analysis was carried out with 2.00 ml. gas samples using a parallelcolumn assembly (Porapak Q. packing in' one leg, 10 ft. x A inch, and Molecular Sieve in the other leg, 4 ft. x A inch) at C. injector 165 C., detector (thermal conductivity, at milliamperes) 240 C., and a helium flow rate of 50 ml./ min.

The results of these runs are shown in Table IV below. Except of the control run, which showed no detectable conversion, eight runs with four solid supports show CO conversions of from 2% to 100%.

TABLE IV Percent Gas- Time on air in catalyst stream, feed contact Percent conver- Catalyst support 1 minutes gas I time 2 sion of C to 002 Molecular sieve 5A, 80/100 mesh 20 1. 7 60% (61, 59). Do. 47 3 2.0 53% (52, 63). Silica gel, grade 12, 28/200 mesh- 15 8 1. 7 2% (2, 2, 2),

D0" 37 7 1.8 44% (43, 44). D0- 61 4 2.0 51% (50, 51). Alumina, chromatographic grade 80/325 mesh 29 100 95% (94 95).

Do- 40 2a 115 100% 4 (100, 100). Charcoal Norbit A," fine powder 47 64 160 100 4 (100, 100). Control (no catalyst)- 5 1 Determined by quantitative gas chromatography of the exit gas.

2 Based upon the estimate that 70% of tubing internal volume is filled by catalyst and solid support: contact time=0.30 x (nominal tube volume)/(flowmeter flow rate).

3 Determined by quantitative gas chromatography; figures in parentheses are replicate individual determinations.

4 No detectable residual 00: threshold of detection is about 0.2% of the feed concentration.

ments.

What is claimed is:

1. The process for oxidizing an oxide (a) selected from the group consisting of CO and S0 to the corresponding oxide (b) CO and S0 respectively, which comprises:

contacting (a) at a temperature of from about 0 C.

to about 100 C. with an aqueous homogeneous solution consisting essentially of (a) a palladium (II) salt having a concentration of metal ion of at least about 0.00005 to about 0.025 mole per liter, said salt being selected from the group consisting of a chloride, bromide, nitrate, sulfate, and Li PdCl (b) a copper (II) chloride or bromide,

(c) a copper (II) salt selected from the group consisting of a nitrate, sulfate, alkylsulfonate, arylsulfonate, tetrafluoroborate, perchlorate, trifluoroacetate, trichloroacetate, and methanephosphonate, and

(d) the balance water,

wherein the total concentration of (b) and (c) in said solution is from about 0.003 to about 3 moles per liter, and wherein the copper (II) chloride or bromide comprises from about 10 to about 80 moles percent of the total of (b) and (c).

2. The process of claim 1, wherein the palladium salt (a) is palladium (II) chloride.

3. The process of claim 1, wherein the concentration of (a) is from about 0.001 to about 0.02 mole per liter.

4. The process of claim 1, wherein (b) is copper (H) chloride.

5. The process of claim 1, wherein the copper (II) salt (c) is copper (II)) nitrate.

6. The process of claim 1, wherein the copper (II) chloride or bromide (b) comprises from about 15 to about 60 mole percent of the total of (b) and (c).

7. The process of claim 1, wherein the palladium (II) salt is Li PdCl 8. The process of claim 7, wherein said solution is aged.

9. The process of claim 1, wherein said aqueous homogeneous solution also contains a chloride or bromide of a Group IA or Group IIA metal.

10. The process of claim 1, wherein(a) is CO and (b) is CO 11. The process of claim 1, wherein (a) is SO; and (b) is S0 12. The process for oxidizing an oxide (21) selected from the group consisting of CO and $0 to the corresponding oxide (b) CO and S0 respectively, which comprises:

5 No detectable CO2; threshold of detection is about 0.3% of the feed concentration of 00 for these expericontacting (a) at a temperature of from about 0 C.

to about 100 C. with a composition consisting essentially of (a) from about 0.0003 to about 0.03 gram-moles of a palladium (II) salt selected from the group consisting of a chloride, bromide, nitrate, sulfate and Li PdCl and (b) from about 0.001 to about 1.5 gram-moles of copper (II) salts,

wherein copper (II) chloride or bromide comprises from about 10 to about mole percent of the total of (b) and a copper (II) salt selected from the group consisting of a nitrate, sulfate, alkylsulfonate, arylsulfonate, tetrafluoroborate, perchlorate, trifluoracetate, trichloroacetate and methanephosphonate.

13. The [process of claim 12, wherein (a) is CO and (b) is CO 14. The process for oxidizing an oxide (a) selected from the group consisting of CO and S0 to the corresponding oxide (b) CO and S0 respectively, which comprises:

contacting (a) at a temperature of from about 0 C. to about 300 C. with a composition deposited upon a carrier, said composition consisting essentially of (a) from about 0.0003 to about 0.03 gram-moles of a palladium (II) salt selected from the group consisting of a chloride, bromide, nitrate, sulfate, and LiPdCl and (b) from about 0.001 to about 1.5 gram-moles of copper (II) salts, wherein copper (II) chloride or bromide comprises from about 10 to about 80 mole percent of the total of (b) and a copper (H) salt selected from the group consisting of a nitrate, sulfate, alkylsulfonate, arylsulfonate, tetrafluoroborate, perchlorate, trifluoroacetate, trichloroacetate and methanephosphonate. 15. The process of claim 14, wherein (a) is CO and (b) is CO References Cited UNITED STATES PATENTS 3,102,919 9/1963 Hirschbeck et a1 423-437 EARL C. THOMAS, Primary Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 790,662 Dated February 5, 1974 Inventgr s WILLIAM G. LLOYD et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Columns 5-6, TABLE II, heading: replace "Pd or Ph" with -Pd or Rh- Columns 9-1-0, TABLE IV, first column, line 9: replace "Norbit". with -Norit Column 9, Claim 12, line 3: replace "S0 with SO Signed and sealed this 16th day of July 1974.

(SEAL) Attest:

MCCOY M. GIBSON, JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents ORM PC4050 (10-69) USCOMM-DC 60376-P69 us. GOVERNMENT PRINTING oFFlc: l9, O366-3l4, 

